Hydrocarbon pyrolysis process



March 17, 1959 LE Rol E. HuTcHlNGs 2,878,252

HYDROCARBON PYROLYSIS PROCESS 2 Sheets-Sheet l Filed Oct. 18, 1956 v .QI mmm zowom QOL. EOL. .hm man. 102mm@ I ,mz3 Sr mmw EBN Sr mz m. .QI Qmm Z` ZOCLmOl l0# EOHbOm N @E Qmm zomom no :Stom

SULLVHSdWSl BHLLVUBdNlL il mmm mbODQOtl Y TI N Nunnl R ET HW O VU T WH M E. m R E L Y B TQI OM ,54 55] METHANE RE GYLE March 17, 1959 Filed Oct. 18, 1956 6 A ETHYLENE LE ROI E. HUTCHINGS HYDROCARBON PYROLYSIS PROCESS 2 Sheets-Sheet 2 ATTORNEY HYDROCARBON PYROLYSIS PROCESSv Le Roi E. Hutchings, Crystal Lake, Ill., assignor to 'lille Pure Oil Company, Chicago, Ill., a corporation of h10 Application October 18, 1956, Serial No. 616,669

9 Claims. (Cl. 260-679),

This invention relates to the pyrolytic processing of low boiling, hydrocarbon feed stocks to produce gaseous hydrocarbons of low molecular weight. It is more specially concerned with the high temperature, thermal de-` composition of selected feed stocks, especially CVC@ hydrocarbons, to produce oleiinic hydrocarbons.

Among the most widely used feed stocks fornumerous` chemical manufacturing processing are the unsaturated hydrocarbons, such as ethylene, propylene, acetylene and others. These unsaturated hydrocarbons can.` be prepared from a variety of petroleum products such as liquefied petroleum gases, naturalgases, waste refinery gases, bu-

tanes, light and heavy naphthas, and distillate stocks of.-

higher boiling range, such as gas oils and the like. Although normally gaseous hydrocarbons are generally `preferred over4 heavier, normally liquid hydrocarbon fractions for pyrolytic treatment, the selection in general depends upon the availability of suitable feed` stocks. Although the normally liquid hydrocarbons can becatalytically decomposed to produce unsaturated, normallyF gaseous hydrocarbons, this type of processing is generally not effective in the treatment of normally gaseousV feed stocks for the production of unsaturatedhydrocarbons because higher temperatures and relatively` short exposure times are required. In processing these feed stocks, it is difficult to maintain catalyst activity and selectivity at high conversions where various equilibriaresult in a plurality of secondary products. Accordingly, more flexible operations within the bounds of practicality and economy can be obtained by utilizing strictly pyrolytic.

methods in the processing ofrselected or prepared feed stocks in the production of normally gaseous,unsaturated the process employed in the pyrolytic treatment of hydro? carbon feed stocks to produce normally gaseous, unsatu-` rated hydrocarbons according to this invention.

2,878,262 Patented Mar. 1.7, 1959 ICC the required temperature level and the heat` for reaction has beensupplied by a variety of pyrolytic techniques.

Accordingtothis invention, steam from the reaction between substantially stoichiometric amounts of hydrogen and oxygen, preferably with an excess of` hydrogen, is produced at sufficiently high temperatures to beemployed as a source of heat for the conversion of hydrocarbon. feed stocks. The hydrocarbon feed stock, which has been heatedfto a temperature somewhat below the range of rapid decomposition, is admixed with the high temperature steamto bring about the desired conversion, em.- ployingvery brief reaction times. The rapidquenching of the reaction eflluentis effected by passing it througha mass of relativelycool, heat-absorbing, granular par-` ticles of i a refractory solid material, and is carried` out. with attendant efficient heat exchange `and recovery. 'Iihe refractory mass in the quenching zone, upon beingheated` to a high` temperature by direct contact with the reaction eluent, is subsequently employed in the regenerative, refractory, thermal processing of a separate stream lof. hydrocarbon feed stock which is introduced directly into theheated'quenching zone to produce unsaturatedgase iFigures 2, 3, and 4 graphically illustrate temperature proliles which occur in the quenching zones employed to rapidly decrease the reaction eiuent below conversion*` level.

Figure 5 schematically illustrates aproduct separation,

In prior art processes, the reactants employed in high4J temperature conversion processes have been heatedto ous hydrocarbons. By employing the integratedprocess of this` invention, the economical pyrolytic productionof unsaturated gaseous hydrocarbons can be carriedout with facility. t

Because the process of this invention can be carried outernploying conventional process equipment, themanipulative operation `is .schematically illustrated by means of` a liow diagram in which auxiliary equipment, such aspumps, valves, et cetera is omitted. With reference `toFigure, l, it is seen` that hydrogen` introduced through line 101mixes with oxygen introduced through line 11, the oxygen preferablybeing substantially pure. When starting up the process, a gas to be used as a source` of heat is prepared=by introducing hydrogen or hydrocarbon fuelgases through line13. These gases are admixediwit'n oxygen` in line` 10.` to. providethe combustible` mixture#vr Once.the process is on stream, however, hydrogen is pro" duced as a by-product of the gas conversion process.` In` this instance, hydrogen isseparated from condensible reaction products, and is transferred to line 10 bymeans i of line 14. The combustiblemixture produced inline 10tburns in combustion zone A. Since the oxygen-hydrogen llame is very hot, the skin of the combustion zone'` is maintained relatively cool by introducingcooling water, low-pressure steam, or feedstock at line 15 bymeans of j which it is introduced intocooling jacket 16 surrounding the combustion zone. If water or steam is used as the coolant, it leavesjacket 16 through line 17 andi enters lineI 10 where it mixes with the burning hydrogen for" further temperature control.v However, ifffeed is used:` as the coolant, it` leaves jacket 16 via line 18. and-mixes with the hot combustion gases in line 19 for conversioni Primary feed enters line 19` by means of line 20.

The mixture of feed gases and hot combustiongases, at a temperature of about Z500-3000 F., enters reaction` zone B wherein pyrolysis occurs. `This zone maybe a" void space, but ispreferably a bed of solid, refractory; heat-exchange pellets which. induce `intimate. mixing andlreduce back-mixing and residence time. 'i

Pyrolytic conversion` of` thehydrocarbon feed.` stock carried out in this manner produces a high yield of olensi without any significant targor. coke formation. By employing steam in a dual capacity as a source of heat for the` conyersionand` as a diluent for lowering the partial pressure, conditions conducive` to undesirable sidehfeac-- tions andcoke formation are avoided andfpractical` yieldsf of unsaturated hydrocarbons Aare obtained.

The hot. products and` combustion gases (which, com?,`

connect reaction zone B with quenching zones C and D, respectively. Quenching zones C and D comprise separate vessels, each containing a mass of a refractory, heattransfer 4material which, when functioning as a quenching. zone, is at a temperature sufficiently low to stop` the ref, action,`e. g., about 300"v F. These parallel zonesserve alternately as the quenching area. When employed as faquenching zone, a hot zone develops in the vessel. and gradually increases in size until a substantial portion vof the refractory mass is at about the reaction temperature which exists in reaction zone B. The temperature of the secondary reaction zone will be about 50e-150 F. Vlower than the temperature in the primaryreaction zone due to heat losses that occur before the heated portion of the bed is employed as a reaction section. The quenchving cycle is arranged so that there is retained in the quenching zone a cool zone of sufficient extent to effect satisfactory cooling of the reaction efluent. `When this situation has been attained, the ow of reaction eiiuent.`

is switched as hereinafter described. The products, which. have Ibeen cooled to a temperature of about 300 F.,' pass from the particular quench zone in service'and mix with hot gases from the other zone. The resulting admixture, which is at a temperature of about 600 to 800 F., is sent to product separation means 24 through lines 25 or 26 and line 27.

In product separator 24, the products are further cooled by direct or indirect heat exchange, as with a spray of water or a temperature-stable solvent, such as. benzene. Solvents of this type may be desirable to selectively absorb one or more components. from the total product gas stream. Products are separated from hydrogen made in the process and withdrawn through line 28. ,Water formed in the combustion zone is discharged through line 29. A portion of the recovered hydrogen is recycled to the combustion zone via line 14, and the remainder is removed through line 30. While quench zone D is on stream, zone C, whic has been heated by reaction products during a previous period, is in use as a secondary reactor. The heat stored in this zone during the previous quench step is used to pyrolyze a secondary hydrocarbon feed entering -at a' temperature of 'about 300 F. through line 31. The pressure on this stream is adjusted to prevent the ow of hot reactants from reaction zone B to secondary reaction zone C through line 22. In practice, a minor portion of this secondary feed flows through line 22 to join line 23, but the major part enters zone C. The secondary feed, upon entering zone C, becomes heated to about the temperature of the zone and pyrolyzes. The pyrolysis reactions are endothermic and further cool the bed, so that it reaches the temperature of the incoming secondary feed, i. e., 300 F., and becomes ready for another quenching'cycle. Pyrolyzed products from zone C flow throughl line 25 to join major productstream 26, by which they are quenched, and the combined products then ow to product recovery system24. When zone D has become hot from quenching the products from f reaction zone B, entry of secondary feed is switched to line 32 and zonefC is changed from reaction to quench service; conversely, zone D isfswitched from quench to reaction service. It is noteworthy that special'valves resistant` to high temperatures are not required for switching this ow. i

The following specie examplesillu'strate this invention:

Example I One hundred and fty pound-moles of product hydrogen and 75 pound-moles of 'substantially' `pure oxygen"y per hour are charged toy a burning section having a cross-sectional area of 3 ysq. ft.' This section consists of a steel vessel lined 'with rebrick, the vessel being ,ventional recovery system. The liquid hydrocarbons are jacketed to provide an annular space throughvwhich cooling vwater may be introduce'rd to prevent the destruc 4 tion of the steel by the .high temperatures. The hydrogen is burned therein and hot combustion gases (steam) are produced. Combustion zone A is maintained at a temperature of 3000 F. by introducing low-pressure steam at the rate of pound-moles per yhour through line 15 into heat-exchange jacket 16. This steam leaves jacket 16 at a temperature of 1000 F. via line 17 and mixes with incoming oxygen and hydrogen to regulate the temperature of the com-bustion products so that a temperature of 2500 F. results when they mix with pound-moles of ethane entering through line 20. The ethane in the hot reaction mixture undergoes pyrolysis in reaction zone B, which comprises va pebble bed contained ina steel tank, the internal walls of which are suitably lined with insulating bricks. The internal diameter of this zone is 1 ft. and the length is 4 ft. After pyrolysis, the products are quenched to 300 F. in zone D. The'quenching zone comprises a similar bed, 3 ft. in diameter and 15 ft. long.

Total time at temperatures at which extensive reactions may take place is about 0.10 second, average. Supplemental ethane is introduced `at line 31 in an amount v approximately equal to that of ethane entering at line y; perature of 2500 F. The remainder of zone C, which was not heated during its quenching cycle, acts as a quenching zone for this material. product streams combine in line 27, and hydrogen and water are separated in product recovery means 24 comprising a vessel 2 ft. in diameter and 10 ft. long in which a spray of water flows down against the rising stream of gases. One thousand gallons of water per hour, at a temperature of 90 F., are passed through the spray nozzle. Uncondensed products pass overhead to a conseparated from the water, and the water is cooled and recrrculated. While the types and quantities of products will vary during the cycles lof the process, the

averages will be as follows:

Moles/100 moles of charge CH4 33 C2H2 26 CZH., 48 03H3 CcHs 3 Higher boiling hydrocarbons 1 Example II Employing the same apparatus as utilized in Example Y ture being regulated with water as in Example I. One

hundred pound-moles of primary feed (ethane) and 100 pound-moles of secondary feed (ethane) are used as i above, and essentially the same products are obtained. In this example, some methane is burned because the product hydrogen is not purified to the extent reached in Example I. Therefore, some carbon dioxide and/or monoxide will be formed in the combustion step, but this is removed dissolved in the water which is condensed and used as cooling spray in the cooling step.

In carrying out the process of this invention, the combustion of oxygen, employing either recycle hydrogen produced during the processing step or hydrogen from a separate source or a hydrocarbon fuel gas, can be carried out `in conventional combustion equipment.

Although the use of substantially pure oxygen is preferred in the combustion step in order to avoid unnecesusd. If pure oxygen is obtained from air, the by-product vThe two resulting nitrogen may be used to react with excess `hydrogenpro-y duced 1n the pyrolysis reactions to make othervaiuable products such as ammonia,` hydrogen cyanide, etcetera.

The 'amount of excess hydrogen produced is dependent` upon heat balances, charge stocks, Yreaction severity, and other process variables, and will limit the amount of nitrogen that may be included in `the oxygen strea-m in the combustion zone, if it is expeditious to do so. Substan-` tially stoichiometric amounts of hydrogen and oxygen,

or an excess of hydrogen, are employed in order to pro-` is available for combustion, a gaseous hydrocarbon fuel such as ethane or propane can -be substituted until the process is on stream.

tCombustion gases issuing from the burner may be at a temperature in excess of 3500? F. Such an excessively high'temperature is undesirable for carrying out the py-` r'olytic conversion of the hydrocarbon feed stock because complete decomposition of the hydrocarbon to carbon andv hydrogen can be prevented only by employing extremely` shot contact times. Accordingly, the combustion gases are preferably cooled to the desired temperature level by dilution with steam just prior to burning the hydrogen and oxygen.A Excess hydrogen may be used for this purpose, also. Suiiicient amounts ofthe coolant must be employed to limit the combustion gases to `about 3000 F. before theycombine with the fresh feed.

T he feed stock, which is introduced into the hot combustion gases issuing from the burner system, can be any selected` or prepared hydrocarbon feed stock which is receptive to thermal decomposition to produce unsaturated, gaseous hydrocarbons. Because the use ofhigh temperature steam as a heat carrier suppresses coke formation to an insignificant level, a wide range of feedstocks istpossible. Accordingly, gaseous feed stocksincluding waste refinery gases, liquefied petroleum gases, natural gas, CZ-Cg saturated hydrocarbons or lmixtures thereof,

or4 lowboiling, normally liquid hydrocarbon fractions, y

cracking temperatures of 2000 to 3000 F. Although the,

steam/hydrocarbon feed mol ratio will depend upon the desired reaction temperature, generally a ratio of 2 to 10V mols of lsteam per mol of hydrocarbon feed will produce desired results. The reaction zone is of conventional design and can be in the form of a simple transfer line wherein the pyrolytic decomposition takes place adiabatically, or in a more elaborate reaction vessel. Suitable reactors include refractory-lined vessels containing a refractory mass which induces intimate mixing of the steam heat-carrier with the feed stock andfreduces 4back-mixing and residence time.

The reaction effluent passes from the reaction zone to a suitable quench zone which, in accordance with this invention, also functions as a heat reservoir. The quench zone preferably is a vessel of requisite diameter containing a heat-absorbing refractory mass. When functioning as a quenching zone, the refractory mass initially is at a temperature suficiently low to permit the quenching of the reaction efuent, e. g., about 300 F. The reaction effluent, upon being quenched, loses its heat to the heattransfer mass which becomes heated to an elevated temperature suicient to induce thermal decomposition. The quenching zone is utilized in such a manner that a cool zone is always maintained in supra position to the secondary reaction Zone to function 'as a quench zone. the temperature suflicient to induce thermal decomposition is reached ina sufficiently long section of the quench Wheny zone, the flow of thereaction eluent is transferred to a second vquench zone connected in parallel with the first` quench zone. As hereinbrfore pointed out, the first quench zone, which has been heated` to a temperature level suiicient to induce pyrolytic decomposition, is then employed asa regenerative refractory system to effect hydrocarbon pyrolysis. The processing of the secondary feed stock is carried-out under substantially the same operating conditionsas employed in the primary reaction Zone,`

temperature of the secondary feed at that temperature by adequate heat exchange. n

Each of the quench zones, or, preferably, secondary reaction vessels, contains several zones at different temperature levels. At the close of a period of quenching service, the temperature prole in the pebble bed is as shown inFigure 2. Thereafter, the vessel is switched to reaction service. Secondary feed is theny admitted, and after a time the temperature profile sho-wn in Figure 3 exists. Entry of secondary feed is stopped before the quench Zone at the top of the secondary reactor has been completely` displaced from the bed, and the vessel is switched to quench service. Midway in the quench period, the temperature proiile is as shown in Figure 4. At this time, the gases leaving thevessel are hot, having been reheatedby the residual hot zone to a temperature below that required to induce pyrolysis. The hot effluent is partially cooled by mixing with quenched eluent from the alternate vessel, which is on reaction service and hasv a profile similar to that shown in Figure 3. Final cooling ofthe combined stream is accomplished by the water or solvent spray, or by indirect heat exchange as previously discussed. 4

When the residual, or spent hot zone has -been entirely displaced, a temperature profile similar to that shown in Figure 2V again exists, and the vessel is again ready for a` period of secondary reactionservice.

The same feed stock employed in the primary reaction system can be utilized, or a different type of feed stock of the same general nature as the primary feedcan be processed in the secondaryy reaction system. It will be noted that this apparatus has a dual function, serving to` quench the reaction effluent emanating from 'the primary reactionzone and functioning as a fixed-bed, regenerative refractory system for the pyrolytic decomposition of (D2-C6 hydrocarbon feed stocks. The construction of such vessels is well known to the art. The effluent passing from the final quench zone is transferred to a product separation zone. There are available a wide choice of methods for separating the cooled reaction effluent into specification products. An illustrative system for the separation of reaction eluent is shown in Figure 5.

In accordance with this illustrative example of a product recovery system, the reactor effluent, after being quenched in the manner hereinbefore described, is sent to a settler 40 in which the water isseparated from the non-condensible constituents, and passes through line 41 into ab- The overhead product from absorber 42 passes via line 50 into a second absorber 51, where incoming lean absorbent oil enters through line S2 to absorb most of the hydrocarbons. The hydrogen resulting from the pyrolysis of hydrocarbons in the reaction section, and some methane, pass overhead from absorber 51 into line 53 from which a portion is returned to the reaction section by line 14, and the balance goes to plant fuel or other uses via lines 54 and 55. The fat oil from absorber 51 passes through line 56 to demethanizer 57 where methane is rejected as an overhead stream. The remaining hydrocarbons pass through line 59 to deethanizer 60 where an overhead stream of ethylene and ethane passes through line 61 into fractionator 62 for separation into ethylene, which leaves lby line 63, and ethane, which leaves by line 64 for recycle to the reaction section.

The hydrocarbons remaining in the liquid in deethanizer 60 pass through line 65 into depropanizer 66 where an overhead stream of propane is taken to storage, or to another process, via line 67. The hydrocarbons heavier than propane are lead through lines 68 and 69, with a portion being withdrawn through line 52 for use as absorption oil in tower 51.

The above description represents one method for obtaining the hydrogen for recycle to the reaction vessel section. A number of other modifications or alternate schemes are possible. Thus, for example, when the hydrocarbon feed is relatively pure ethane, and reaction conditions are such as to give virtually complete conversion of. the ethane, ethane-cthylene fractionator 52 may be omitted, since the overhead product from deethanizer 60 would be ethylene of sufficient purity for many uses.

As another modification, if the reaction conditions are such as to give only a minor amount of acetylene, acetylene absorber 42 and'fractionators 45 and 47 may Ibe omitted, and instead, the acetylene content of the products may be controlled by means of a conventional acetylene hydrogenation unit which then treats all of the gases passing through line 41.

In general, the cooled reaction eiuent is settled to separate the water and hydrocarbon constituents. The gaseous product from the settler is then sent to the compression system and/or absorption system. In this section, conventional techniques like those described above are employed to separate the gaseous constituents to provide the desired gaseous products in vsubstantially pure form, as well as recy-cle hydrogen.

Accordingly, it is seen that the subject process provides a flexible pyrolytic process for the decomposition of hydrocarbon feed stocks to normally gaseous, unsaturated hydrocarbons. Important features of this invention are high heat utilization, simple product purification, absence of requirements for external heat supply or fuel, and process design which avoids the use of special valves for high temperature applications.

Accordingly, I claim as my invention:

l. In the non-catalytic high temperature continuous gas pyrolysis of C2-C6 saturated hydrocarbons to produce unsaturated hydrocarbons and hydrogen, a reaction cycle which comprises continuously burning recycled hydrogen with oxygen to provide an oxygen-free Hue gas consisting essentially of superheated steam, continuously mixing a C2-C6 hydrocarbon feed stock with said steam in a reaction zone to produce a pyrolysis eflluent containing unsaturated hydrocarbons and hydrogen, passing said pyrolysis eiuent into a first quenching chamber packed with a relatively cool mass of granular refractory heat transfer material, the rate of flow of reactants and rate of cooling in said quench chamber being such that thehydrocarbons are maintained at pyrolysis temperature for only a fraction of a second, terminating the flow of pyrolysis effluent through said quench chamber when the interface between hot and cool portions of the, refractory packing has reached a point where the remaining.

cool portion of the packing is at about minimum efficiency for quenchingthe pyrolysis efiuent, transferring thejiow,

of pyrolysis `efiiuent through a second quench chamber packed with a relatively cool mass of granularrefractory heat transfer material to quench said effluentvv at,the sameV rate as in said first chamber, and simultaneously therewith passing a cool secondary Cz-C hydrocarbon,4 feed stock through said first quench chamber to pyrolyze the same to produce a secondary pyrolysis efliuent containing unsaturated hydrocarbons and cool the heated mand fio'w of said secondary hydrocarbon feed to said portion of said first quench chamber packing, rapidly.

cooling said secondary pyrolysis effluent below pyrolysis temperatura-mixing the efuents from said quench chambers, separating the mixed efliuents into a hydrogen fraction, a mixed hydrocarbonfraction, and a water fraction, and recycling the hydrogen fraction to the hydrogencombustion step, continuing to pass primary pyrolysis etliuent into said second quench chamber and secondary hydro-j carbon feed into said first quench chamber until the interface between heated and cool portions of refractory pack,-`

ing in said second quench chamber reaches a point where the cool portion of packing is at about minimum etli-` ciency` for quenching pyrolysis eflluent and the hot portion is at substantially the temperature of the primary `pyrolysis effluent, and the heated portion of said`- first quench chamber packing has been cooled to substantially the temperature of the secondary hydrocarbon feed, and

then transferring flow of primary pyrolysis effluent to said first quench chamber for continuing rapid quenching second quench chamberfor continuing pyrolysis. l

V2. In the non-catalytic high temperature continuous gas pyrolysis of C2-C6 saturated hydrocarbons to pro-- duce unsaturated hydrocarbons and hydrogen, a reaction .g cycle which comprises continuously burning recycled hyf l, xsaid steam in a reaction zone at a temperature of about between hot and cool portions of the refractory pack-.,

2000-3000 F. to produce a pyrolysis efluent containing unsaturated hydrocarbons and hydrogen, passing said v pyrolysis eluent into a first quenching chamber packed with a relatively cool mass of granular refractory heat transfer material, the rate of liow of reactants and .rate of cooling in said quench chamber being such-that the,A hydrocarbons are maintained at pyrolysis temperature for v about 0.00\1-0.1 second, terminating the fiow of pyrolysis efiluent through said quench chamber when the interface ing has reached a point where the remaining cool portion of the packing is at about minimum efiiciency for quenching the pyrolysis effluent, transferring the ow of pyrolysis effluent through a second quench chamber vpacked with a relatively cool mass of granular refracl tory heat transfer material to quench said effluent atthe same rate as in said first chamber, and simultaneouslytherewith passing a cool secondary C2-C6 hydrocarbon feed stock through said first quench chamber at a contact time of 0.001-0.1 second to pyrolyze the same lto produce a secondarypyrolysis effluent containing unsaturated hydrocarbons and cool the heated portion of sad`first quench chamber packing, rapidly cooling said secondarypyrolysis effluent below pyrolysis temperature, mixing the effluents from said quench chambers, further cooling the mixed efuents to preclude undesirable side reactions,

separating the mixed efiiuents into a hydrogen fraction, a mixed hydrocarbon fraction, anda water fraction, and recycling the hydrogen fraction to the hydrogen combustion step, continuing to pass primary pyrolysis effluent into, said second quench chamber and sec- .f ondary hydrocarbon feed into said first quench chamber until the interface between heated and cool portions of refractory' packing in said second' quench chamber has reachedapoint where the coolf portion of packing is'4 at about minimum efciency for quenching pyrolysis eluent and the hot portion is at substantially the temper ature of the primary pyrolysis efuent, and the heated portion of said first quench chamber packing has been cooled to substantially the temperature of the secondary hydrocarbon feed, then transferring flow of primary pyrolysis eflluent to said first quench chamber for continuing rapid quenching and ow of said secondary hydrocarbon feed to said second quench chamber for continuing pyrolysis, and thereafter repeating the cycle.

3. A process in accordance with claim 2 in which the tempering of said hot flue gas is effected by admixing suitable amounts of low pressure steam.

4, A process in accordance with claim 2 in which the tempering of said hot ilue gas is effected by indirect heat exchange with a uid selected from the group of water, steam, said primary feed, and liquid hydrocarbons.

5. A process in accordance with claim 2 in which said primary and said secondary feeds have substantially the same composition.

6. A process in accordance with claim 2 in which the quenching of the secondary reaction efuent is initially effected in the residual cold section of said first quenching zone, and thereafter, when said residual cold section is eliminated, by commingling said secondary efuent with the quenched, primary reaction efuent.

7. A process in accordance with claim 6 in which said secondary hydrocarbon feed stock consists essentially of ethane.

8. A process in accordance with claim 4 in which said feeds are introduced at a temperature of about 300 F.

9. In the non-catalytic high temperature continuous gas pyrolysis of a hydrocarbon feed stock consisting essentially of ethane to produce unsaturated hydrocarbons and hydrogen, a reaction cycle which comprises continuously burning recycled hydrogen with oxygen to provide an oxygen-free flue gas consisting essentially of superheated steam, tempering said steam to a temperature of about 25003000 F. by mixing low temperature steam therewith, continuously mixing said hydrocarbon feed stock with said steam in a reaction zone comprising a mass of granular heat exchange material at 20003000 F. to produce a pyrolysis effluent containing unsaturated hydrocarbons and hydrogen, passing said pyrolysis efuent into a rst quenching chamber packed with a relatively cool mass of granular refractory heat transfer material, the rate of flow of reactants and rate of cooling in said quench chamber being such that the hydrocarbon feed stock is 10 maintained at pyrolysis temperature for about 0.001-01 second, terminating the flow of pyrolysis effluent through said quench chamber when the interface between hot and cool portions of the refractory packing has reached a point where the remaining cool portion of the packing is at about minimum eiciency for quenching the pyrolysis effluent, transferring the flow of pyrolysis effluent through a second quench chamber packed with a relatively cool mass of granular refractory heat transfer material to quench said emuent at the same rate as in said first chamber, and simultaneously therewith passing a cool secondary hydrocarbon feed stock consisting essentially of ethane through said first quench chamber at a contact time of (LOGI-0.1 second to pyrolyze the same to produce a secondary pyrolysis effluent containing unsaturated hydrocarbons and cool the heated portion of said rst quench chamber packing, rapidly cooling said secondary pyrolysis effluent below pyrolysis temperature, mixing the effluents from said quench chamber, further cooling the mixed efuents to preclude undesirable side reactions, separating the mixed eluents into a hydrogen fraction, a mixed hydrocarbon fraction, and a water fraction, and recycling the hydrogen fraction to the hydrogen combustion step, continuing to pass primary pyrolysis eiiluent into said second quench chamber and secondary hydrocarbon feed into said first quench chamber until the interface between heated and cool portions of refractory packing in said second quench chamber reaches a point where the cool portion of packing is at about minimum efficiency for quenching pyrolysis eflluent and the hot portion is at substantially the temperature of the primary pyrolysis effluent, and the heated portion of said `first quench chamber packing has been cooled to sub- References Cited in the file of this patent UNITED STATES PATENTS 2,363,716 Wolk NOV. 28, 1944- 2,608,594 Robinson Aug. 26, 1952 2,692,819 Hasche et al. IOct. 26, 1954 

1. IN THE NON-CATALYTIC HIGH TEMPERATURE CONTINUOUS GAS PYROLYSIS OF C2-C6 SATURATED HYDROCARBONS TO PRODUCE UNSATURATED HYDROCARBONS AND HYDROGEN, A REACTION CYCLE WHICH COMPRISES CONTINUOUSLY BURNING RECYCLED HYDROGEN WITH OXYGEN TO PROVIDE AN OXYGEN-FREE FLUE GAS CONSISTING ESSENTIALLY OF SUPERHEATED STEAM, CONTINUOUSLY MIXING A C2-C6 HYDROCARBON FEED STOCK WITH SAID STEAM IN A REACTION ZONE TO PRODUCE A PYROLYSIS EFFUENT CONTAINING UNSATURATED HYDROCARBONS AND HYDROGEN, PASSING SAID PYROLYSIS EFFUENT INTO A FIRST QUENCHING CHAMBER PACKED WITH A RELATIVELY COOL MASS OF GRANULAR REFRACTORY HEAT TRANSFER MATERIAL, THE RATE OF FLOW OF REACTANTS AND RATE OF COOLING IN SAID QUENCH CHAMBER BEING SUCH THAT THE HYDROCARBONS ARE MAINTAINED AT PYROLYSIS TEMPERATURE FOR ONLY A FRACTION OF A SECOND, TERMINATING THE FLOW OF PYROLYSIS EFFUENT THROUGH SAID QUENCH CHAMBER WHEN THE INTERFACE BETWEEN HOT AND COOL PORTIONS OF THE REFRACTORY PACKING HAS REACHED A POINT WHERE THE REMAINING COOL PORTION OF THE PACKING IS AT ABOUT MINIMUM EFFICIENCY FOR QUENCHING THE PYROLYSIS EFFUENT, TRANSFERRING THE FLOW OF PYROLYSIS EFFLUENT THROUGH A SECOND QUENCH CHAMBER PACKED WITH A RELATIVELY COOL MASS OF GRANULAR REFRACTORY HEAT TRANSFER MATERIAL TO QUENCH SAID EFFLUENT AT THE SAME RATE AS IN SAID FIRST CHAMBER, AND SIMULTANEOUSLY THEREWITH PASSING A COOL SECONDARY C2-C6 HYDROCARBON FEED STOCK THROUGH SAID FIRST QUENCH CHAMBER TO PYROLYZE THE SAME TO PRODUCE A SECONDARY PYROLYSIS EFFLUENT CONTAINING UNSATURATED HYDROCARBONS AND COOL THE HEATED PORTION OF SAID FIRST QUENCH CHAMBER PACKING, RAPIDLY COOLING SAID SECONDARY PYROLYSIS EFFLUENT BELOW PYROLYSIS TEMPERATURE, MIXING THE EFFLUENTS FROM SAID QUENCH CHAMBERS; SEPARATING THE MIXED THE EFFLUENTS INTO A HYDROGEN FRACTION, A MIXED HYDROCARBON FRACTION, AND A WATER FRACTION, AND RECYCLING THE HYDROGEN FRACTION TO THE HYDROGEN COMBUSTION STEP, CONTINUING TO PASS PRIMARY PYROLYSIS EFFLUENT INTO SAID SECOND QUENCH CHAMBER AND SECONDARY HYDROCARBON FEED INTO SAID FIRST QUENCH CHAMBER UNTIL THE INTERFACE BETWEEN HEATED AND COOL PORTIONS OF REFRACTORY PACKING IN SAID SECOND QUENCH CHAMBER REACHES A POINT WHERE THE COOL PORTION OF PACKING IS AT ABOUT MINIMUM EFFICIENCY FOR QUENCHING PYROLYSIS EFFLUENT AND THE HOT PORTION IS AT SUBSTANTIALLY THE TEMPERATURE OF THE PRIMARY PYROLYSIS EFFLUENT, AND THE HEATED PORTION OF SAID FIRST QUENCH CHAMBER PACKING HAS BEEN COOLED TO SUBSTANTIALLY THE TEMPERATURE OF THE SECONDARY HYDROCARBON FEED, AND THEN TRANSFERRING FLOW OF PRIMARY PYROLYSIS EFFLUENT TO SAID FIRST QUENCH CHAMBER FOR CONTINUING RAPID QUENCHING AND FLOW OF SAID SECONDARY HYDROCARBON FEED TO SAID SECOND QUENCH CHAMBER FOR CONTINUING PYROLYSIS. 